CN112939891A - Method for preparing biphenyl benzothiazole compound - Google Patents

Method for preparing biphenyl benzothiazole compound Download PDF

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CN112939891A
CN112939891A CN202110201995.8A CN202110201995A CN112939891A CN 112939891 A CN112939891 A CN 112939891A CN 202110201995 A CN202110201995 A CN 202110201995A CN 112939891 A CN112939891 A CN 112939891A
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biphenyl
benzothiazole compounds
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benzothiazole
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CN112939891B (en
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李红喜
王昊
李海燕
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2

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Abstract

The invention discloses a preparation method of a biphenyl benzothiazole compound. The invention takes N- (2-bromophenyl) alkylthioamide such as N- (2-bromophenyl) alkylthioamide derivatives and the like as raw materials, takes sodium phosphate as alkali, and prepares the biphenyl benzothiazole compound by a one-pot method.

Description

Method for preparing biphenyl benzothiazole compound
Technical Field
The invention belongs to the technical field of organic chemical synthesis methodology, and particularly relates to a preparation method of a biphenyl benzothiazole compound.
Background
Biphenyl benzothiazole compounds can be prepared from 2-substituted benzothiazoles. Prior art in the presence of visible or UV light in [ Ru (bpy) ]3]2+，[Ir(ppy)3]The 2-substituted benzothiazole compounds are prepared under the catalysis of transition metal complexes or organic photosensitizers, the reactions often increase additional equipment, reagents or separation cost, and toxic heavy metals or organic pollutants can be introduced.
Disclosure of Invention
In order to overcome the technical problems, the invention discloses a brand-new visible light-promoted one-pot method for preparing biphenyl benzothiazole compounds from N- (2-bromophenyl) thioamide. Specifically, the invention adopts the following technical scheme:
a preparation method of a biphenyl benzothiazole compound comprises the following steps of carrying out intramolecular cross coupling reaction on N- (2-bromophenyl) thioamide as a raw material under the irradiation of visible light and in the presence of alkali to prepare a benzothiazole compound; and then, preparing the biphenyl benzothiazole compound by taking the benzothiazole compound and phenylboronic acid as raw materials through catalytic reaction.
The biphenyl benzothiazole compound is prepared by a one-pot method, after intramolecular cross coupling reaction is finished, phenylboronic acid, a catalyst and potassium carbonate are directly added without purification, and heating is carried out for catalytic reaction, so that the biphenyl benzothiazole compound is obtained.
In the invention, the intramolecular cross coupling reaction is carried out at room temperature for 2-5 hours; the intramolecular cross coupling reaction is carried out in a solvent under the protection of inert gas.
In the present invention, the molar ratio of the N- (2-bromophenyl) thioamide to the base is 1 (0.2 to 0.8), preferably 1:0.2 to 0.5, and most preferably 1: 0.5.
In the invention, the N- (2-bromophenyl) thioamide and the benzothiazole compounds respectively have the following structural general formulas:
Figure DEST_PATH_IMAGE001
、
Figure 453427DEST_PATH_IMAGE002
wherein R is4Selected from fluorine, chlorine, bromine, iodine, methyl, methoxy, tert-butyl or trifluoromethyl.
In the invention, the catalytic reaction is carried out in the presence of a palladium catalyst and potassium carbonate in a solvent and in an inert gas. The temperature of the catalytic reaction is 100-120 ℃, and the time is 3-6 hours.
In the invention, the inert gas is selected from any one of nitrogen, helium, neon and argon, preferably nitrogen; the alkali is any one of inorganic alkali, the inorganic alkali is any one of sodium phosphate, sodium carbonate, potassium hydroxide, sodium hydroxide and sodium acetate, and sodium phosphate is preferred; the solvent is dimethyl sulfoxide (DMSO), DMF, Tetrahydrofuran (THF), methanol, ethanol, acetonitrile (MeCN), etc.
The technical scheme of the invention can be expressed as follows:
Figure DEST_PATH_IMAGE003
the reaction for preparing the benzothiazole compound is carried out under the condition of no photosensitizer or transition metal catalyst, so that the problem that an auxiliary (transition) catalyst is needed in the prior art is effectively solved; the reaction can be carried out by simple 45W household compact fluorescent lamp irradiation, and unexpected technical effect is achieved. Furthermore, the biphenyl benzothiazole compound is effectively prepared by utilizing the benzothiazole compound, the whole process is green, efficient and easy to operate, and the method is a good method for synthesizing the benzothiazole compound.
Detailed Description
The invention discloses a method for preparing benzothiazole compounds by using N- (2-bromophenyl) thioamide promoted by visible light, which comprises the following steps: adding the reactants into a reaction container with a stirring device under the protection of inert gas according to the molar ratio of N- (2-bromophenyl) thioamide to inorganic base =1:0.5, adding dimethyl sulfoxide, and stirring and reacting for 2-5 hours at room temperature under the irradiation of a 45W household compact fluorescent lamp to obtain the benzothiazole compound. The method does not need other reagents and reaction steps, and can simply and efficiently obtain the benzothiazole compound. The stirring device is a magnetic stirring device; the reaction vessel is a sealed reaction tube.
In the invention, the bromine site in the N- (2-bromophenyl) thioamide reacts with the sulfur site to prepare the benzothiazole compound, and the reaction is clear. The invention will be further described with reference to specific embodiments. Unless otherwise indicated, reagents, materials, instruments and the like used in the following examples are commercially available. The reaction of the benzothiazole compound is carried out in the absence of a photosensitizer or a transition metal catalyst, and only N- (2-bromophenyl) thioamide, inorganic base and DMSO are used as raw materials; the reaction of the present example was carried out at room temperature using a 45W household compact fluorescent lamp as the visible light source. The specific experiment and test method of the invention is conventional technology.
Example 1: visible light promotes the reaction of the N- (2-bromophenyl) thiobenzamide.
Figure 432884DEST_PATH_IMAGE004
N- (2-bromophenyl) thiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and then silica gel chromatography thin layer chromatography is carried out to obtain the target product, wherein the separation yield is 98% and the HPLC yield is 99%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.09–8.07 (m, J = 7.7 Hz, 3H), 7.90 (d, J = 7.9 Hz, 1H), 7.49 (m, 4H), 7.38 (t, J = 7.5 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 168.1, 154.2, 135.1, 133.6, 131.0, 129.0, 127.6, 126.3, 125.2, 123.2, 121.6。
On the basis of the above experiment, the following experiment was obtained by varying the single conditions:
mixing Na3PO4Change to Na2CO3Or Et3N, the rest is unchanged, and the HPLC yields of the products are 86% and 87%, respectively.
The substituent bromine was replaced with chlorine, the remainder was unchanged, and the product was obtained in 24% yield by HPLC.
The following examples relate to isolated yields of the products.
Example 2: the visible light promotes the reaction of the N- (2-bromophenyl) -4-chlorothiobenzamide.
Figure DEST_PATH_IMAGE005
N- (2-bromophenyl) -4-chlorothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 93%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.05 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 7.8 Hz, 2H), 7.87 (d, J = 7.8 Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 7.43 (d, J = 7.9 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.6, 154.1, 137.0, 135.1, 132.1, 129.3, 128.7, 126.5, 125.4, 123.3, 121.7。
Example 3: the visible light promotes the reaction of the N- (2-bromophenyl) -4-bromothiobenzamide.
Figure 18148DEST_PATH_IMAGE006
N- (2-bromophenyl) -4-bromothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 91%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.05 (d, J = 8.0 Hz, 1H), 7.93 (d, J = 8.1 Hz, 2H), 7.88 (d, J = 7.8 Hz, 1H), 7.60 (d, J = 8.1 Hz, 2H), 7.49 (t, J = 7.4 Hz, 1H), 7.38 (t, J = 7.2 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.8, 154.2, 135.2, 132.7, 132.4, 129.1, 126.7, 125.6, 125.6, 123.5, 121.8。
Example 4: the visible light promotes the reaction of the N- (2-bromophenyl) -4-iodothiobenzamide.
Figure DEST_PATH_IMAGE007
N- (2-bromophenyl) -4-iodothiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 86%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.06 (d, J = 8.1 Hz, 1H), 7.89 (d, J = 7.8 Hz, 1H), 7.86–7.78 (m, 4H), 7.50 (t, J = 7.5 Hz, 1H), 7.40 (t, J = 7.4 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.8, 154.1, 138.2, 135.0, 133.1, 128.9, 126.5, 125.5, 123.3, 121.7, 97.5。
The DMSO was replaced with a mixture of 1 mL THF and 1 mL acetonitrile, and the remainder was unchanged, resulting in a product yield of 39%.
Example 5: the visible light promotes the reaction of the N- (2-bromophenyl) -4-trifluoromethyl-thiobenzamide.
Figure 334728DEST_PATH_IMAGE008
Will N- (2-bromophenyl) -4-trifluoromethylthiobenzamide (0.2 mmol), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 24 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. After the reaction is finished, 4 mL of water is added, then the mixture is extracted by 3X 4 mL of ethyl acetate, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and filtered, and after the filtrate is subjected to rotary evaporation and concentration, the target product is obtained by thin layer chromatography separation of silica gel chromatography, and the yield is 94%.
1H NMR (400 MHz, CDCl3, ppm) δ 8.19 (d, J = 7.9 Hz, 2H), 8.10 (d, J = 8.1 Hz, 1H), 7.92 (d, J = 7.9 Hz, 1H), 7.74 (d, J = 8.0 Hz, 2H), 7.52 (t, J = 7.6 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H)。13C NMR (101 MHz, CDCl3, ppm) δ 166.0, 154.1, 136.8, 135.2, 132.5 (q, 2 J C-F = 32.8 Hz, 1H), 127.8, 126.7, 126.0 (q, 3 J C-F = 3.8 Hz, 5H), 125.8, 123.8 (q, 1 J C-F = 272.3 Hz, 1H) 123.6, 121.8。19F NMR (377 MHz, CDCl3, ppm) δ -62.8。
Example 6
Figure DEST_PATH_IMAGE009
N- (2-bromophenyl) -4-iodothiobenzamide (58.4 mg, 0.2 mmol, 1.0 equiv), Na3PO4(0.1 mmol), and DMSO (2 mL) were added to a dry reaction tube with a magnetic stirrer, followed by N2The reaction was stirred for 5 h under irradiation of a 45W household compact fluorescent lamp with 3 replacements. Then, Pd (OAc) was added under a nitrogen atmosphere2(0.5 mg, 0.002 mmol, 1 mol%), phenylboronic acid (29.3 mg, 0.24 mmol, 1.2 equivalents), K2CO3(55.3 mg, 0.4 mmol, 2.0 equiv.) was added to the reaction solution, and stirred at 110 deg.CAnd reacting for 5 hours. After the reaction is finished, the reaction mixture is cooled to room temperature, 4 mL of water is added, then 3X 4 mL of ethyl acetate is used for extraction, organic phases are combined, the organic phases are dried by anhydrous sodium sulfate, filtration is carried out, filtrate is subjected to rotary evaporation and concentration, and separation is carried out through silica gel chromatography thin layer chromatography to obtain the target product biphenyl benzothiazole compound, and white solid is 48.5 mg.
1H NMR (400 MHz, CDCl3, ppm) δ 8.16 (d, J = 7.6 Hz, 2H), 8.09 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 7.8 Hz, 1H), 7.72 (d, J = 7.6 Hz, 2H), 7.65 (d, J = 7.2 Hz, 2H), 754–7.43 (m, 3H), 7.43–7.35 (m, 2H). 13C NMR (101 MHz, CDCl3, ppm) δ 167.7, 154.2, 143.7, 140.1, 135.1, 132.5, 128.9, 128.0, 128.0, 127.6, 127.1, 126.4, 125.2, 123.2, 121.6. m.p. = 192.3–193.3 °C. HRMS (ESI) m/z [M + H]+ Calcd for C19H14NS+ 288.0841; Found 288.0852。
The DMSO was replaced with a mixed solution of 1 mL THF and 1 mL methanol, and the remainder was unchanged, and a white product, biphenyl benzothiazole compound, was not obtained.
The whole reaction process is green, efficient and easy to operate, is a good method for synthesizing the benzothiazole compounds, and can further react with phenylboronic acid to obtain the biphenyl benzothiazole compounds.

Claims (10)

1. A method for preparing biphenyl benzothiazole compounds is characterized by comprising the following steps of carrying out intramolecular cross coupling reaction on N- (2-bromophenyl) thioamide as a raw material under the irradiation of visible light and in the presence of alkali to prepare benzothiazole compounds; and then, preparing the biphenyl benzothiazole compound by taking the benzothiazole compound and phenylboronic acid as raw materials through catalytic reaction.
2. The method for preparing biphenyl benzothiazole compounds according to claim 1, wherein the intramolecular cross-coupling reaction is a reaction at room temperature for 2 to 5 hours; the intramolecular cross coupling reaction is carried out in a solvent under the protection of inert gas.
3. The method for preparing biphenyl benzothiazole compounds according to claim 1, wherein the molar ratio of N- (2-bromophenyl) thioamide to base is 1 (0.2 to 0.8).
4. The method for preparing biphenyl benzothiazole compounds according to claim 1, wherein said N- (2-bromophenyl) thioamide has the following general structural formula:
Figure 309445DEST_PATH_IMAGE001
wherein R is4Selected from fluorine, chlorine, bromine, iodine, methyl, methoxy, tert-butyl or trifluoromethyl.
5. The method for producing biphenyl benzothiazole compounds according to claim 1, wherein the catalytic reaction is carried out in the presence of palladium catalyst, potassium carbonate, solvent and inert gas.
6. The method for preparing biphenyl benzothiazole compounds according to claim 1, wherein the temperature of the catalytic reaction is 100 to 120 ℃ and the time is 3 to 6 hours.
7. The method for preparing biphenyl benzothiazole compounds according to claim 1, wherein the inert gas is selected from any one of nitrogen, helium, neon and argon.
8. The method for producing biphenyl benzothiazole compounds according to claim 1, wherein the base is any one selected from the group consisting of sodium phosphate, sodium carbonate, potassium hydroxide, sodium hydroxide, and sodium acetate.
9. The method for preparing biphenyl benzothiazole compounds according to claim 1, wherein the solvent is dimethylsulfoxide, DMF, tetrahydrofuran, methanol, ethanol or acetonitrile.
10. The biphenyl benzothiazole compounds according to claim 1, which are prepared by the process for preparing biphenyl benzothiazole compounds.
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WO2022178736A1 (en) * 2021-02-24 2022-09-01 苏州大学 Method for preparing biphenyl benzothiazole compound

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CN102153593A (en) * 2011-02-21 2011-08-17 四川大学 Red light organic electroluminescent phosphorescent iridium compound

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CN102153593A (en) * 2011-02-21 2011-08-17 四川大学 Red light organic electroluminescent phosphorescent iridium compound

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Title
VASUDEVAN DHAYALAN等: "Synthesis of 2-arylbenzothiazole derivatives based on activated carbon/oxygen oxidation followed by Suzuki-Miyaura coupling", 《SYNTHESIS》 *
W RUSSELL BOWMA等: "INTRAMOLECULAR AROMATIC SUBSTITUTION (SRN1) REACTIONS，USE OF ENTRAINMINT FOR TIIE PREPARATION OF BENZOTHIAZOLES", 《TETRAHEDRON LETTERS》 *

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WO2022178736A1 (en) * 2021-02-24 2022-09-01 苏州大学 Method for preparing biphenyl benzothiazole compound

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